Metallocene compositions

ABSTRACT

This invention relates to metallocene compositions and their use in the preparation of catalyst systems for olefin polymerization, particularly propylene polymerization. 
     In one embodiment, the metallocenes of the present invention may be represented by the formula:                    
     wherein: 
     M is a metal of Group 4, 5, or 6 of the Periodic Table; 
     R 1  and R 2  are identical or different, and are one of a hydrogen atom, a C 1 -C 10  alkyl group, a C 1 -C 10  alkoxy group, a C 6 -C 10  aryl group, a C 6 -C 10  aryloxy group, a C 2 -C 40  alkenyl group, a C 7 -C 40  arylalkyl groupa C 7 -C 40  alkylaryl group, a C 8 -C 40  arylalkenyl group, or a halogen atom, or are a conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30 atoms not counting hydrogen; 
     R 5  and R 6  are identical or different, are one of a hydrogen atom, a halogen atom, a C 1 -C 10  alkyl group, which may be halogenated, a C 6 -C 10  aryl group, which may be halogenated, a C 2 -C 10  alkenyl group, a C 7 -C 40  arylalkyl group, a C 7 -C 40  alkylaryl group, a C 8 -C 40  arylalkenyl group, a —NR 2   15 , —SR 15 , —OR 15 , —OSiR 3   15  or —PR 2   15  radical, wherein: R 15  is one of a halogen atom, a C 1 -C 10  alkyl group, or a C 6 -C 10  aryl group; 
     R 7  is                    
     wherein: 
     R 17  to R 24  are as defined for R 1  and R 2 , or two or more adjacent radicals R 17  to R 24 , including R 20  and R 21 , together with the atoms connecting them form one or more rings; 
     M 2  is carbon, silicon, germanium or tin; 
     the radicals R 3 , R 4 , and R 10  are identical or different and have the meanings stated for R 5  and R 6 ; or two adjacent R 10  radicals can be joined together to form a ring system.

This application is based on U.S. Provisional Patent Application Ser.No. 60/215,597 filed Jun. 30, 2000.

FIELD

This invention relates to metallocene compositions and their use in thepreparation of catalyst systems for olefin polymerization, particularlypropylene polymerization.

BACKGROUND

The use of metallocene compositions in olefin polymerization is wellknown. Metallocenes containing substituted, bridged indenyl derivativesare noted for their ability to produce isotactic propylene polymershaving high isotacticity and narrow molecular weight distribution.Considerable effort has been made toward obtaining metallocene producedpropylene polymers having ever-higher molecular weight and meltingpoint, while maintaining suitable catalyst activity.

Toward this end it has been found that there is a direct relationshipbetween the way in which a metallocene is substituted, and the molecularstructure of the resulting polymer. For the substituted, bridged indenyltype metallocenes, it is now well established that the type andarrangement of substituents on the indenyl groups, as well as the typeof bridge connecting the indenyl groups, determines such polymerattributes as molecular weight and melting point. Unfortunately, it isimpossible at this time to accurately correlate specific substitution orbridging patterns with specific polymer attributes, though trends may beidentified.

For example, U.S. Pat. No.5,840,644 describes certain metallocenescontaining aryl-substituted indenyl derivatives as ligands, which aresaid to provide propylene polymers having high isotacticity, narrowmolecular weight distribution and very high molecular weight.

Likewise, U.S. Pat. No. 5,936,053 describes certain metallocenecompounds said to be useful for producing high molecular weightpropylene polymers. These metallocenes have a specific hydrocarbonsubstituent at the 2 position and an unsubstituted aryl substituent atthe 4 position, on each indenyl group of the metallocene compound.

WO 98/40419 and WO 99/42497 both describe certain supported catalystsystems for producing propylene polymers having high melting point.Metallocene compositions and their activators are often combined with asupport material in order to obtain a catalyst system that is lesslikely to cause reactor fouling. However, it is known that supportedmetallocene catalyst systems tend to result in a polymer having lowermelting point than would otherwise be obtained if the metallocene werenot supported.

Much of the current research in this area has been directed toward usingmetallocene catalyst systems under commercially relevant processconditions, to obtain propylene polymers having melting points higherthan known metallocene catalyst systems and close to, or as high as,propylene polymers obtained using conventional, Ziegler-Natta catalystsystems, i.e., 160° C. or higher. The present inventors have discoveredmetallocene compounds that have this capability.

SUMMARY

The present invention relates generally to metallocene compoundsrepresented by the formula:

wherein:

M is a metal of Group 4, 5, or 6 of the Periodic Table preferably,zirconium, hafnium and titanium, most preferably zirconium;

R¹ and R² are identical or different, preferably identical, and are oneof a hydrogen atom, a C₁-C₁₀ alkyl group, preferably a C₁-C₃ alkylgroup, a C₁-C₁₀ alkoxy group, preferably a C₁-C₃ alkoxy group, a C₆-C₁₀aryl group, preferably a C₆-C₈ aryl group, a C₆-C₁₀ aryloxy group,preferably a C₆-C₈ aryloxy group, a C₂-C₁₀ alkenyl group, preferably aC₂-C₄ alkenyl group, a C₇-C₄₀ arylalkyl group, preferably a C₇-C₁₀arylalkyl group, a C₇-C₄₀ alkylaryl group, preferably a C₇-C₁₂ alkylarylgroup, a C₈-C₄₀ arylalkenyl group, preferably a C₈-C₁₂ arylalkenylgroup, or a halogen atom, preferably chlorine; or a conjugated dienewhich is optionally substituted with one or more hydrocarbyl,tri(hydrocarbyl)silyl groups or hydrocarbyl,tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30atoms not counting hydrogen;

R⁵ and R⁶ are identical or different, preferably identical, are one of ahydrogen atom, a halogen atom, preferably a fluorine, chlorine orbromine atom, a C₁-C₁₀ alkyl group, preferably a C₁-C₄ alkyl group,which may be halogenated, a C₆-C₁₀ aryl group, which may be halogenated,preferably a C₆-C₈ aryl group, a C₂-C₁₀ alkenyl group, preferably aC₂-C₄ alkenyl group, a C₇-C₄₀ arylalkyl group, preferably a C₇-C₁₀arylalkyl group, a C₇-C₄₀ alkylaryl group, preferably a C₇-C₁₂ alkylarylgroup, a C₈-C₄₀ arylalkenyl group, preferably a C₈-C₁₂ arylalkenylgroup, a —NR₂ ¹⁵, —SR¹⁵, —OR¹⁵, —OSiR₃ ¹⁵ or —PR₂ ¹⁵ radical,

wherein:

R¹⁵ is one of a halogen atom, preferably a chlorine atom, a C₁-C₁₀ alkylgroup, preferably a C₁-C₃ alkyl group, or a C₆-C₁₀ aryl group,preferably a C₆-C₉ aryl group;

R⁷ is

wherein:

R¹⁷ to R²⁴ are as defined for R¹ and R², or two or more adjacentradicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with the atomsconnecting them form one or more rings;

M² is carbon, silicon, germanium or tin;

the radicals R³, R⁴, and R¹⁰ are identical or different and have themeanings stated for R⁵ and R⁶, or two adjacent R¹⁰ radicals are joinedtogether to form a ring, preferably a ring containing from about 4-6carbon atoms.

More specifically, the present invention relates generally tometallocene compounds represented by the formula:

wherein:

M¹ is selected from the group consisting of titanium, zirconium,hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;

R¹ and R² are identical or different and are one of a hydrogen atom, aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀aryloxy group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀ alkenyl group, a C₇-C₄₀arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group,an OH group or a halogen atom; or a conjugated diene which is optionallysubstituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groupsor hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said dienehaving up to 30 atoms not counting hydrogen;

R³ are identical or different and are each a hydrogen atom, a halogenatom, a C₁-C₁₀ alkyl group which may be halogenated, a C₆-C₁₀ aryl groupwhich may be halogenated, a C₂-C₁₀ alkenyl group, a C₇-C₄₀-arylalkylgroup, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group, a —NR′₂,—SR′, —OR′, —OSiR′₃ or —PR′₂ radical, wherein: R′ is one of a halogenatom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group;

R⁴ to R⁷ are identical or different and are hydrogen, as defined for R³or two or more adjacent radicals R⁵ to R⁷ together with the atomsconnecting them form one or more rings;

R¹³ is represented by the formula:

wherein:

R¹⁷ to R²⁴ are defined for R¹ and R², or two or more adjacent radicalsR¹⁷ to R^(24,) including R²⁰ and R²¹, together with the atoms connectingthem form one or more rings;

M² is carbon, silicon, germanium or tin;

R⁸, R⁹, R¹⁰ R¹¹ and R¹² are identical or different and have the meaningsstated for R⁴ to R⁷.

The present invention further relates to metallocene catalyst systemscomprising one or more or the above compounds and one or more activatorsor cocatalysts, and optionally, support material, and to the use of suchmetallocene catalyst systems in olefin polymerization, particularlypropylene polymer polymerization.

DESCRIPTION

In one embodiment, the metallocenes of the present invention may berepresented by the formula:

wherein:

M is a metal of Group 4, 5, or 6 of the Periodic Table preferably,zirconium, hafnium and titanium, most preferably zirconium;

R¹ and R² are identical or different, preferably identical, and are oneof a hydrogen atom, a C₁-C₁₀ alkyl group, preferably a C₁-C₃ alkylgroup, a C₁-C₁₀ alkoxy group, preferably a C₁-C₃ alkoxy group, a C₆-C₁₀aryl group, preferably a C₆-C₈ aryl group, a C₆-C₁₀ aryloxy group,preferably a C₆-C₈ aryloxy group, a C₂-C₁₀ alkenyl group, preferably aC₂-C₄ alkenyl group, a C₇-C₄₀ arylalkyl group, preferably a C₇-C ₁₀arylalkyl group, a C₇-C₄₀ alkylaryl group, preferably a C₇-C₁₂ alkylarylgroup, a C₈-C₄₀ arylalkenyl group, preferably a C₈-C₁₂ arylalkenylgroup, or a halogen atom, preferably chlorine; R¹ and R² may also bejoined together to form an alkanediyl group or a conjugated C₄₋₄₀ dieneligand which is coordinated to M¹ in a metallocyclopentene fashion; R¹and R² may also be identical or different conjugated dienes, optionallysubstituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groupsor hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said dieneshaving up to 30 atoms not counting hydrogen and forming a π complex withM, examples include, but are not limited to: 1,4-diphenyl-1,3-butadiene,1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,4-hexadiene,1-phenyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene,1,4-ditolyl-1,3-butadiene, 1,4-bis(trimethylsilyl)-1,3-butadiene, and1,4-dinaphthyl-1,3-butadiene.

R⁵ and R⁶ are identical or different, preferably identical, are one of ahydrogen atom, a halogen atom, preferably a fluorine, chlorine orbromine atom, a C₁-C₁₀ alkyl group, preferably a C₁-C₄ alkyl group,which may be halogenated, a C₆-C₁₀ aryl group, which may be halogenated,preferably a C₆-C₈ aryl group, a C₂-C₁₀ alkenyl group, preferably aC₂-C₄ alkenyl group, a C₇-C₄₀-arylalkyl group, preferably a C₇-C ₁₀arylalkyl group, a C₇-C₄₀ alkylaryl group, preferably a C₇-C₁₂ alkylarylgroup, a C₈-C₄₀ arylalkenyl group, preferably a C₈-C₁₂ arylalkenylgroup, a —NR₂ ¹⁵, —SR¹⁵, —OR¹⁵, —OSiR₃ ¹⁵ or —PR₂ ¹⁵ radical,

wherein:

R¹⁵ is one of a halogen atom, preferably a chlorine atom, a C₁-C₁₀ alkylgroup, preferably a C₁-C₃ alkyl group, or a C₆-C₁₀ aryl group,preferably a C₆-C₉ aryl group;

R⁷ is

wherein:

R¹⁷ to R²⁴ are as defined for R¹ and R², or two or more adjacentradicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with the atomsconnecting them form one or more rings;

M² is carbon, silicon, germanium or tin; and

the radicals R³, R⁴, and R¹⁰ are identical or different and have themeanings stated for R⁵ and R⁶, or two adjacent R¹⁰ radicals are joinedtogether to form a ring, preferably a ring containing from about 4-6carbon atoms.

Particularly preferred metallocenes of the present invention arerepresented by the formula:

wherein:

M¹ is selected from the group consisting of titanium, zirconium,hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten,preferably zirconium, hafnium or titanium, most preferably zirconium;

R¹ and R² are identical or different, and are one of a hydrogen atom, aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀aryloxy group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀ alkenyl group, a C₇-C₄₀arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group,an OH group or a halogen atom, or are a conjugated diene which isoptionally substituted with one or more hydrocarbyl,tri(hydrocarbyl)silyl groups or hydrocarbyl,tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30atoms not counting hydrogen;

preferably R¹ and R² are identical and are a C₁-C₃ alkyl or alkoxygroup, a C₆-C₈ aryl or aryloxy group, a C₂-C₄ alkenyl group, a C₇-C₁₀arylalkyl group, a C₇-C₁₂ alkylaryl group, or a halogen atom, preferablychlorine;

R³ are identical or different and are each a hydrogen atom, a halogenatom, a C₁-C₁₀ alkyl group which may be halogenated, a C₆-C₁₀ aryl groupwhich may be halogenated, a C₂-C₁₀ alkenyl group, a C₇-C₄₀ -arylalkylgroup, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group, a —NR′₂,—SR′, —OR′, —OSiR′₃ or —PR′₂ radical, wherein: R′ is one of a halogenatom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group; preferably R³ is nota hydrogen atom;

preferably each R³ is identical and is a fluorine, chlorine or bromine,atom, a C₁-C₄ alkyl group which may be halogenated, a C₆-C₈ aryl groupwhich may be halogenated, a —NR′₂, —SR′, —OR′, —OSiR′₃ or —PR′₂ radical,wherein: R′ is one of a chlorine atom, a C₁-C₄ alkyl group, or a C₆-C₈aryl group;

R⁴ to R⁷ are identical or different and are hydrogen, as defined for R³or two or more adjacent radicals R⁵ to R⁷ together with the atomsconnecting them form one or more rings;

R¹³ is represented by the formula:

wherein:

R¹⁷ to R²⁴ are as defined for R¹ and R², or two or more adjacentradicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with the atomsconnecting them form one or more rings; preferably, R¹⁷ to R²⁴ arehydrogen.

M² is carbon, silicon, germanium or tin, preferably silicon; and

R⁸, R⁹, R¹⁰, R¹¹ and R¹² are identical or different and have themeanings stated for R⁴ to R⁷.

As utilized herein, the term “alkyl”, alone or in combination, means astraight-chain or branched-chain alkyl radical. Examples of suchradicals include, but are not limited to, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl,hexyl, octyl and the like. The term “alkenyl” means a straight-chain orbranched-chain hydrocarbon radial having one or more double bonds.Examples of suitable alkenyl radicals include, but are not limited to,ethenyl, propenyl, allyl, 1,4-butadienyl and the like. The term “alkoxy”means an alkyl ether radical wherein: the term alkyl is as definedabove. Examples of suitable alkyl ether radicals include, but are notlimited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,iso-butoxy, sec-butoxy, tert-butoxy and the like. The term “aryl” meansa phenyl, azulenyl, or naphthyl radical and the like which optionallycontains a heteroatom and/or carries one or more substituents, forexample, alkyl, alkoxy, halogen, hydroxy, amino, nitro etc.

The following are particularly preferred metallocenes:

rac-9-silafluorendiyl(2-methyl-4-phenylindenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-ethyl-4-phenylindenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-propyl-4-phenylindenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-propyl-4-phenylindenyl)₂zirconiumdichloride;

rac-9-silafluorendiyl(2-n-butyl-4-phenylindenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-butyl-4-phenylindenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-sec-butyl-4-phenylindenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-tert-butyl-4-phenylindenyl)₂zirconiumdichloride;

rac-9-silafluorendiyl(2-methyl-4-phenylindenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-ethyl-4-phenylindenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-propyl-4-phenylindenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-propyl-4-phenylindenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-butyl-4-phenylindenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-butyl-4-phenylindenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-sec-butyl-4-phenylindenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-tert-butyl-4-phenylindenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-methyl-4-phenylindenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-ethyl-4-phenylindenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-propyl-4-phenylindenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl-4-phenylindenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-butyl-4-phenylindenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl-4-phenylindenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl-4-phenylindenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl-4-phenylindenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-methyl-4-phenylindenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-ethyl-4-phenylindenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-propyl-4-phenylindenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl-4-phenylindenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-butyl-4-phenylindenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl-4-phenylindenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl-4-phenylindenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl-4-phenylindenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)2hafnium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-propyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-propyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafniumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafniumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium θ⁴-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene; and

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconiumθ⁴-1,4-diphenyl-1,3-butadiene.

“9-silafluorendiyl-” refers to the substituent:

The metallocenes of this invention are prepared according to generaltechniques known from the literature, for example U.S. Pat. Nos.5,789,634 and 5,840,644 (both entirely incorporated herein byreference).

Generally, metallocenes of this type are synthesized as shown belowwhere (R⁴═H) (a) is an aryl-coupling reaction between a4-halosubstituted indene and an aryl Grignard catalyzed byNiCl2(PPh3)2in ether-type solvents at room temperature to reflux.Product is usually purified by column chromatography or distillation.(b) is a deprotonation via a metal salt of an alkyl anion (e.g. n-BuLi)to form an indenide followed by reaction with an appropriate bridgingprecursor as specified in the examples. Reactions are usually done inether-type solvents at ambient temperatures. The final product ispurified by column chromatography or distillation. (c) is doubledeprotonation via an alkyl anion (e.g. n-BuLi) to form a dianionfollowed by reaction with a metal halide (e.g. ZrCl₄). The reaction areusually done in ether-type or aromatic solvents at ambient temperatures.The final products are obtained by recrystallization of the crudesolids.

The metallocenes of this invention are highly active catalyst componentsfor the polymerization of olefins. The metallocenes are preferablyemployed as chiral racemates. However, it is also possible to use thepure enantiomers in the (+) or (−) form. The pure enantiomers allow anoptically active polymer to be prepared. However, the meso form of themetallocenes should be removed, since the polymerization-active center(the metal atom) in these compounds is no longer chiral due to themirror symmetry at the central metal atom and it is therefore notpossible to produce a highly isotactic polymer. If the meso form is notremoved, atactic polymer is formed in addition to isotactic polymer. Forcertain applications this may be entirely desirable.

Rac/meso metallocene isomer separation is facilitated when metallocenescontaining certain bridging groups are prepared. We have found this tobe true when the bridging group, R¹³, is represented by the formula:

wherein:

M² and R¹⁷ to R²⁴ are as defined above.

Metallocenes are generally used in combination with some form ofactivator in order to create an active catalyst system. The terms“activator” and “cocatalyst” are used interchangeably and are definedherein to mean any compound or component, or combination of compounds orcomponents, capable of enhancing the ability of one or more metallocenesto polymerize olefins. Alklyalumoxanes such as methylalumoxane (MAO) arecommonly used as metallocene activators. Generally alkylalumoxanescontain 5 to 40 of the repeating units:

R(AlRO)_(x)AIR₂ for linear species

and

(AlRO)_(x)for cyclic species

where R is a C₁-C₈ alkyl including mixed alkyls. Compounds in which R ismethyl are particularly preferred. Alumoxane solutions, particularlymethylalumoxane solutions, may be obtained from commercial vendors assolutions having various concentrations. There are a variety of methodsfor preparing alumoxane, non-limiting examples of which are described inU.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,103,031 and EP-A-0 561 476, EP-B1-0 279 586,EP-A-0 594-218 and WO 94/10180, each fully incorporated herein byreference.

Ionizing activators may also be used to activate metallocenes. Theseactivators are neutral or ionic, or are compounds such astri(n-butyl)ammonium tetrakis(pentaflurophenyl)borate, which ionize theneutral metallocene compound. Such ionizing compounds may contain anactive proton, or some other cation associated with, but not coordinatedor only loosely coordinated to, the remaining ion of the ionizingcompound. Combinations of activators may also be used, for example,alumoxane and ionizing activator combination, see for example, WO94/07928.

Descriptions of ionic catalysts for coordination polymerizationcomprised of metallocene cations activated by non-coordinating anionsappear in the early work in EP-A-0 277 003, EP-A-0 277 004 and U.S. Pat.No. 5,198,401 and WO-A-92/00333 (each incorporated herein by reference).These teach desirable methods of preparation wherein: metallocenes areprotonated by an anion precursor such that an alkyl/hydride group isabstracted from a transition metal to make it both cationic andcharge-balanced by the non-coordinating anion. Suitable ionic saltsinclude tetrakis-substituted borate or aluminum salts having fluoridedaryl-constituents such as phenyl, biphenyl and napthyl.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to said cation or which is only weakly coordinated tosaid cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral fourcoordinate metallocene compound and a neutral by-product from the anion.Non-coordinating anions useful in accordance with this invention arethose which are compatible, stabilize the metallocene cation in thesense of balancing its ionic charge at +1, yet retain sufficientlability to permit displacement by an ethylenically or acetylenicallyunsaturated monomer during polymerization.

The use of ionizing ionic compounds not containing an active proton butcapable of producing both the active metallocene cation and anon-coordinating anion is also known. See, for example, EP-A-0 426 637and EP-A-0 573 403 (each incorporated herein by reference). Anadditional method of making the ionic catalysts uses ionizing anionprecursors which are initially neutral Lewis acids but form the cationand anion upon ionizing reaction with the metallocene compounds, forexample the use of tris(pentafluorophenyl) borane. See EP-A-0 520 732(incorporated herein by reference). Ionic catalysts for additionpolymerization can also be prepared by oxidation of the metal centers oftransition metal compounds by anion precursors containing metallicoxidizing groups along with the anion groups, see EP-A-0 495 375(incorporated herein by reference).

Where the metal ligands include halogen moieties (for example,bis-cyclopentadienyl zirconium dichloride) which are not capable ofionizing abstraction under standard conditions, they can be convertedvia known alkylation reactions with organometallic compounds such aslithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignardreagents, etc. See EP-A-0 500 944 and EP-A1-0 570 982 (each incorporatedherein by reference) for in situ processes describing the reaction ofalkyl aluminum compounds with dihalo-substituted metallocene compoundsprior to or with the addition of activating anionic compounds.

Methods for supporting ionic catalysts comprising metallocene cationsand NCA are described in WO 9950311, U.S. Pat. Nos. 5,643,847 and5,972,823, U.S. patent application No. 09184358, filed Nov. 2, 1998 andU.S. patent application Ser. No. 09184389, filed Nov. 2, 1998 (eachfully incorporated herein by reference).

When the activator for the metallocene supported catalyst composition isa NCA, preferably the NCA is first added to the support compositionfollowed by the addition of the metallocene catalyst. When the activatoris MAO, preferably the MAO and metallocene catalyst are dissolvedtogether in solution. The support is then contacted with theMAO/metallocene catalyst solution. Other methods and order of additionwill be apparent to those skilled in the art.

The catalyst systems used to prepare the compositions of this inventionare preferably supported using a porous particulate material, such asfor example, talc, inorganic oxides, inorganic chlorides such asmagnesium chloride, and resinous materials such as polyolefin orpolymeric compounds.

Preferably, the support materials are porous inorganic oxide materials,which include those from the Periodic Table of Elements of Groups 2, 3,4, 5, 13 or 14 metal/metalloid oxides. Silica, alumina, silica-alumina,and mixtures thereof are particularly preferable. Other inorganic oxidesthat may be employed either alone or in combination with the silica,alumina or silica-alumina are magnesia, titania, zirconia, and the like.

Preferably the support material is porous silica which has a surfacearea in the range of from 10 to 700 m²/g, a total pore volume in therange of from 0.1 to 4.0 cc/g and an average particle size in the rangeof from 10 to 500 μm. More preferably, the surface area is in the rangeof from 50 to 500 m²/g, the pore volume is in the range of from 0.5 to3.5 cc/g and the average particle size is in the range of from 20 to 200μm. Most desirably the surface area is in the range of from 100 to 400m²/g, the pore volume is in the range of from 0.8 to 3.0 cc/g and theaverage particle size is in the range of from 30 to 100 μm. The averagepore size of typical porous support materials is in the range of from 10to 1000 Å. Preferably, a support material is used that has an averagepore diameter of from 50 to 500 Å, and most desirably from 75 to 350 Å.It may be particularly desirable to dehydrate the silica at atemperature of from 100° C. to 800° C. anywhere from 3 to 24 hours.

The metallocene, activator and support material may be combined in anynumber of ways. More than one metallocene may also be used. Examples ofsuitable support techniques are described in U.S. Pat. Nos. 4,808,561and 4,701,432 (each fully incorporated herein by reference.). Preferablythe metallocenes and activator are combined and their reaction productsupported on the porous support material as described in U.S. Pat. No.5,240,894 and WO 94/28034, WO 96/00243, and WO 96/00245 (each fullyincorporated herein by reference.) Alternatively, the metallocenes maybe preactivated separately and then combined with the support materialeither separately or together. If the metallocenes are separatelysupported, then preferably, they are dried then combined as a powderbefore use in polymerization.

Regardless of whether the metallocene(s) and their activator areseparately precontacted or whether the metallocene(s) and activator arecombined at once, in some instances it may be preferred that the totalvolume of reaction solution applied to porous support is less than 4times the total pore volume of the porous support, more preferably lessthan 3 times the total pore volume of the porous support and even morepreferably in the range of from more than 1 to less than 2.5 times thetotal pore volume of the porous support. Procedures for measuring thetotal pore volume of porous support are well known in the art. One suchmethod is described in Volume 1, Experimental Methods in CatalystResearch, Academic Press, 1968, pages 67-96.

The supported catalyst system may be used directly in polymerization orthe catalyst system may be prepolymerized using methods well known inthe art. For details regarding prepolymerization, see U.S. Pat. Nos.4,923,833 and 4,921,825, and EP 0 279 863 and EP 0 354 893 (each fullyincorporated herein by reference).

The metallocene catalyst systems described herein are useful in thepolymerization of all types of olefins. This includes polymerizationprocesses which produce homopolymers, copolymers, terpolymers and thelike as well as block copolymers and impact copolymers. Thesepolymerization processes may be carried out in solution, in suspensionor in the gas phase, continuously or batchwise, or any combinationthereof, in one or more steps, preferably at a temperature of from 60°C. to 200° C., more preferably from 30° C. to 80° C., particularlypreferably from 50° C. to 80° C. The polymerization or copolymerizationis carried out using olefins of the formula R^(a)CH═CH-R^(b). In thisformula, R^(a) and R^(b) are identical or different and are a hydrogenatom or an alkyl radical having 1 to 14 carbon atoms. However, R^(a) andR^(b) may alternatively form a ring together with the carbon atomsconnecting them. Examples of such olefins are ethylene, propylene,1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, norbornene andnorbornadiene. In particular, propylene and ethylene are polymerized.The metallocenes and metallocenes catalyst systems of this invention aremost suitable for the polymerization of propylene based polymers.

If necessary, hydrogen is added as a molecular-weight regulator and/orin order to increase the activity. The overall pressure polymerizationsystem is from 0.5 to 100 bar. Polymerization is preferably carried outin the industrially particularly interesting pressure range from 5 to 64bar.

Typically, the metallocene is used in the polymerization in aconcentration, based on the transition metal, of from 10⁻³ to 10⁻⁸ mol,preferably from 10⁻⁴ to 10⁻⁷ mol, of transition metal per dm³ of solventor per dm³ of reactor volume. When alumoxane is used as the cocatalyst,it is used in a concentration of from 10⁻⁵ to 10⁻¹ mol, preferably from10⁻⁴ to 10⁻²mol, per dm³ of solvent or per dm³ of reactor volume. Theother cocatalysts mentioned are used in an approximately equimolaramount with respect to the metallocene. In principle, however, higherconcentrations are also possible.

If the polymerization is carried out as a suspension or solutionpolymerization, an inert solvent which is customary for the Zieglerlow-pressure process is typically used for example, the polymerizationis carried out in an aliphatic or cycloaliphatic hydrocarbon; examplesof which are propane, butane, hexane, heptane, isooctane, cyclohexaneand methylcyclohexane. It is also possible to use a benzene orhydrogenated diesel oil fraction. Toluene can also be used. Thepolymerization is preferably carried out in the liquid monomer. If inertsolvents are used, the monomers are metered in gas or liquid form.

Before addition of the catalyst, in particular of the supported catalystsystem, another alkylaluminum compound, such as, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,trioctylaluminum or isoprenylaluminum, may additionally be introducedinto the reactor in order to render the polymerization system inert (forexample to remove catalyst poisons present in the olefin). This compoundis added to the polymerization system in a concentration of from 100 to0.01 mmol of Al per kg of reactor contents. Preference is given totriisobutylaluminum and triethylaluminum in a concentration of from 10to 0.1 mmol of Al per kg of reactor contents. This allows the molarAl/M¹ ratio to be selected at a low level in the synthesis of asupported catalyst system.

In principle, however, the use of further substances for catalysis ofthe polymerization reaction is unnecessary, i.e. the systems accordingto the invention can be used as the only catalysts for thepolymerization of olefins.

The process according to the invention is distinguished by the fact thatthe metallocenes described can give propylene polymers of very highmolecular weight, melting point, and very high stereotacticity, withhigh catalyst activities in the industrially particularly interestingpolymerization temperature range of from 50° C. to 80° C.

The catalyst systems of this invention are capable of providingpolymers, particularly propylene homopolymers and copolymers, ofexceptionally high molecular weight and melting point even when used inprocesses under commercially relevant conditions of temperature,pressure and catalyst activity. Preferred melting points are at least ashigh as 155° C., more preferably at least 157° C., even more preferablyat least 157° C., and most preferably 160° C. or more.

The catalyst systems of this invention are also capable of providingpropylene polymers having high stereospecificity and regiospecificity.Isotactic propylene polymers prepared according to the processes of thisinvention may have a proportion of 2-1-inserted propene units of lessthan 0.5%, at a triad tacticity of greater than 98%. Preferably there isno measurable proportion of 2-1 -inserted propene units. Triad tacticityis determined using ¹³C-NMR according to J. C. Randall, Polymer SequenceDetermination: Carbon-13 NMR Method, Academic Press New York 1978.Polymers prepared using the processes of described herein find uses inall applications including fibers, injection-molded parts, films, pipesetc.

While the present invention has been described and illustrated byreference to particular embodiments, it will be appreciated by those ofordinary skill in the art, that the invention lends itself to manydifferent variations not illustrated herein. For these reasons, then,reference should be made solely to the appended claims for purposes ofdetermining the true scope of the present invention.

Although the appendant claims have single appendencies in accordancewith U.S. patent practice, each of the features in any of the appendantclaims can be combined with each of the features of other appendantclaims or the main claim.

EXAMPLES

All air sensitive experiments are carried out in nitrogen purged dryboxes. All solvents were purchased from commercial sources.4-Bromo-2-methyl indene, 4-chloro-2-methyl-indene and tris(perfluorophenyl) borane in toluene were purchased from commercialsources. Aluminum alkyls were purchased as hydrocarbon solutions fromcommercial sources. The commercial methylalumoxane (“MAO”) was purchasedfrom Albemarle as a 30 wt % solution in toluene. The metallocenesracemic dimethylsiladiyl(2-methyl4-phenylindenyl)₂ zirconium dichlorideand racemic dimethylsiladiyl(4-[1-naphthy]-2-methylindenyl)₂ zirconiumdichloride were obtained from commercial sources.

Comparative Example 1 racemicdimethylsiladiyl(2-methyl-4-phenylindenyl)₂zirconium dichlorideSupported Comparison Metallocene Catalyst System 1 racemicdimethylsiladiyl(2-methyl-4-phenylindenyl)₂zirconium dichloride/MAO

In a 100 mL round bottom flask racemicdimethylsiladiyl(2-methyl4-phenylindenyl)₂ zirconium dichloride(Comparison metallocene 1, 0.055 g) was added to a MAO solution (6.74 g,7.2 mL) and stirred twenty minutes. This was filtered through a mediumglass frit funnel and washed with toluene (14 mL). To the combinedfiltrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C. dehydration). This slurry was stirred for twenty minutes then driedat 40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was further dried a total of abouttwo hours and twenty two minutes. The supported catalyst was recoveredas a light orange, free flowing solid (5.63 g).

Comparative Example 2 racemic dimethylsiladiyl(2-methyl-4-[1-naphthy]indenyl)₂zirconium dichloride Supported ComparisonMetallocene Catalyst System 2 racemic dimethylsiladiyl(2-methyl-4-[1-naphthy]indenyl)₂zirconium dichloride/MAO

In a 100 mL round bottom flask racemic dimethylsiladiyl(2-methyl-4-[1-naphthy]indenyl)₂ zirconium dichloride (Comparisonmetallocene 2, 0.064 g) was added to a MAO solution (6.74 g, 7.2 mL) andstirred twenty minutes. This was filtered through a medium glass fritfunnel and washed with toluene (14 mL). To the combined filtrates wasadded dehydrated silica (4.0 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for twenty minutes then dried at40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was further dried a total of abouttwo hours. The supported catalyst was recovered as an orange, freeflowing solid (4.72 g).

Example 3 racemic[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-methylindene]zirconiumdichloride 4-[3′,5′-di-t-butylphenyl]-2-methylindene

4-Chloro-2-methylindene (6.1 g, 37 mmol) and NiCl₂(PPh₃)₂ (1.8 g, 2.8mmol) were dissolved in 150 mL of Et₂O. 3,5-Di-t-butylphenylmagnesiumbromide (10 g, 37 mmol) as a Et₂O solution was added to the solution andthe reaction was stirred overnight at room temperature. After overnightstirring, the reaction was slowly quenched with H₂O to neutralizeunreacted Grignard. The solution was subsequently treated with 100 mL of10% HCl(aq), neutralized with saturated sodium bicarbonate aqueoussolution. The organic layer was dried with magnesium sulfate and thesolvent was removed by rotary evaporation. The remaining residue wasloaded onto a silica gel column and eluted with hexane. Yield was 4.6 g(40%).

lithium 4-[3′,5′-di-t-butylphenyl]-2-methylindene

4-[3′,5′-Di-t-butylphenyl]-2-methylindene (4.7 g, 15 mmol) was dissolvedin 80 mL of pentane. To this solution was added 5.9 mL of n-BuLi (2.5Min hexane) and the reaction is allowed to stir 4 hours at roomtemperature. A white solid precipitated from solution and was collectedby frit filtration and washed with additional pentane. Yield was 3.6 g(78%).

9-silafluorenebis[4-(3′,5′-di-t-butylphenyl)-2-methylindene

9,9-Dichloro-9-silafluorene (1.2 g, 9.2 mmol) was dissolved in 80 mL ofTHF. To this solution was slowly added lithium4-(3′,5′-di-t-butylphenyl)-2-methylindene (3.0 g, 9.2 mmol) as a drypowder and the solution was stirred overnight. After this time, thesolvent was removed in vacuo and the residue was taken up in diethylether. The solution was filtered through a frit to remove LiCl and thesolvent was removed in vacuo and used as a crude product (4.1 g) for thenext step.

[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-methylindene]ZrCl₂

The crude solid from the previous step (4.1 g, 5.5 mmol) was taken up in50 mL of diethyl ether. To this solution was slowly added n-BuLi (4.4mL, 2.5 M in hexane) and stirred for 3 hours at room temperature. Thesolution was cooled to −30° C. and ZrCl₄ (1.28 g, 4.6 mmol) was added asa dry powder and stirred at room temperature for 2 hours. The solventwas removed in vacuo and toluene was added to the crude residue. Thesolution was filtered to remove LiCl. The filtrate was concentrated andpentane is added under heating. The solution was cooled to inducecrystallization. Yield of pure racemic isomer was 187 mg (3.7%).

Supported Metallocene Catalyst System 3 racemic[9-silafluorenebis(4(3′,5′-di-t-butylphenyl)-2-methylindene]zirconiumdichloride

In a 100 mL round bottom flask racemic[9-Silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-methylindene]zirconiumdichloride (0.085 g) was added to a MAO solution (6.74 g, 7.2 mL) andstirred twenty minutes. This was filtered through a medium glass fritfunnel and washed with toluene (14 mL). To the combined filtrates wasadded dehydrated silica (4.0 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for twenty minutes, then dried at40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was further dried a total of abouttwo hours and twenty minutes. The supported catalyst was recovered as apink reddish, free flowing solid (5.24 g).

Example 4 racemic[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindene]zirconiumdichloride 4-[3′,5′-di-t-butylphenyl]-2-isopropylindene

4-Chloro-2-isopropylindene (7.2 g, 37 mmol) and NiCl₂(PPh₃)₂ (1.8 g, 2.8mmol) were dissolved in 150 mL of Et₂O. 3,5-Di-di-t-butylphenylmagnesiumbromide (10 g, 37 mmol) as a Et₂O solution was added to the solution andthe reaction was stirred overnight at room temperature. After overnightstirring, the reaction was slowly quenched with H₂O to neutralizeunreacted Grignard. The solution was subsequently treated with 100 mL of10% HCl(aq), neutralized with saturated sodium bicarbonate aqueoussolution. The organic layer was dried with magnesium sulfate and thesolvent was removed by rotary evaporation. The remaining residue wasloaded onto a silica gel column and eluted with hexane. Yield is 5.8 g(45%).

lithium 4-[3′,5′-di-t-butylphenyl]-2-isopropylindene

4-[3′,5′-di-t-butylphenyl]-2-isopropylindene (5.8 g, 17 mmol) wasdissolved in 80 mL of pentane. To this solution was added 6.6 mL ofn-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours atroom temperature. A white solid precipitated from solution and wascollected by frit funnel filtration and washed with additional pentane.Yield is 5.0 g (87%).

silafluorenebis[4-(3′,5′-bis[t-butyl]phenyl)-2-isopropylindene

9,9-Dichloro-9-silafluorene (1.1 g, 8.5 mmol) was dissolved in 80 mL ofTHF. To this solution was slowly added lithium4-(3′,5′-di-t-butylphenyl)-2-isopropylindene (3.0 g, 8.5 mmol) as a drypowder and the solution was stirred overnight. After this time, thesolvent was removed in vacuo and the residue was taken up in diethylether. The solution as filtered through frit to remove LiCl and thesolvent was removed in vacuo and used as a crude product (3.9 g) for thenext step.

9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindene]ZrCl₂

The crude solid from the previous step (3.9 g, 4.6 mmol) was taken up in50 mL of diethyl ether. To this solution was slowly added n-BuLi (3.7mL, 2.5 M in hexane) and stirred for 3 hours at room temperature. Thesolution was cooled to −30° C. and ZrCl₄ (1.1 g, 4.6 mmol) was added asa dry powder and stirred at room temperature for 2 hours. The solventwas removed in vacuo and toluene was added to the crude residue. Thesolution was filtered to remove LiCl. The filtrate was concentrated andpentane added under heating. The solution was cooled to inducecrystallization. Yield of pure racemic isomer was 280 mg (6.0%)

Supported Metallocene Catalyst System 4 racemic[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindene]zirconiumdichloride

In a 100 mL round bottom flask racemic[[9-Silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindene]zirconiumdichloride (0.090 g) was added to a MAO solution (6.74 g, 7.2 mL) andstirred twenty minutes. This was filtered through a medium glass fritfunnel and washed with toluene (14 mL). To the combined filtrates wasadded dehydrated silica (4.0 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for twenty minutes, then dried at40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated and then the solid was further dried a total of abouttwo hours and twenty minutes. The supported catalyst was recovered as alight purple, free flowing solid (5.17 g).

Example 5[9-silafluorenebis(4-(3′,5′-dimethylphenyl)2-isopropylindene]zirconiumdichloride 2,2′-Dibromobiphenyl

To a stirred solution of o-dibromobenzene (47.3 g, 0.2 mol) in 450 mL ofanhydrous THF was added 76.4 mL of n-BuLi (1.0M in Et₂O). Theo-dibromobenzene solution was cooled in a dry ice/acetone bath. Theyellow-green reaction mixture was allowed to warm to 5° C. and was thenhydrolyzed with 100 mL of 5% hydrochloric acid. The resulting layerswere separated and the aqueous layer extracted 4 times with 4×20 mLportions of diethyl ether. The ether washings were combined with theoriginal organic layer and dried over sodium sulfate, filtered, andconcentrated by distillation until the distillation temperature reached70° C. The residue was treated with 50 mL of absolute ethanol and cooledto give 2,2′-dibromobiphenyl. Yield was 2.32 g (7.4%)

9,9-Dichloro-9-silafluorene

Lithium wire (3.33 g, 0.08 mol) was washed with pentane, carefully cutinto small pieces, and suspended in 150 mL of Et₂O. While stirring,2,2-dibromobiphenyl (25 g, 0.08 mol) in 100 mL of diethyl ether wasadded dropwise over 1 hour and the contents were allowed to stir for 10hours. The mixture was filtered through a frit to remove any unreactedLi and LiBr. The filtrate was loaded into an addition funnel and slowlydropped into a solution containing SiCl₄ (50 g, 0.08 mol) in 200 mL ofEt₂O. After addition, the contents were stirred at room temperature for5 hours. The solvent was removed in vacuo and 300 mL of pentane wasadded. The solution was filtered to remove LiCl and the solvents wereagain removed in vacuo. The solids were then loaded into a sublimatorand allowed to sublime at 150° C. under full vacuum. Yield was 10.0 g(51%).

4-(3′,5′-dimethylphenyl)-2-isopropylindene

4-chloro-2-isopropylindene (10 g, 54 mmol) and NiCl₂(PPh₃)₂ (1.8 g, 2.8mmol) were dissolved in 150 mL of Et₂O. 3,5-Dimethylphenylmagnesiumbromide (54 mmol) as a Et₂O solution was added under vigorous stirringand the reaction was stirred overnight at room temperature. Afterovernight stirring, the reaction was slowly quenched with H₂O toneutralize unreacted Grignard. The solution was subsequently treatedwith 100 mL of 10% HCl(aq), and neutralized with saturated sodiumbicarbonate aqueous solution. The organic layer was dried with magnesiumsulfate and the solvent was removed by rotary evaporation. The remainingresidue was loaded onto a silica gel column and eluted with hexane.Yield was 5.5 g (39%).

lithium 4-(3′,5′-dimethylphenyl)2-isopropylindene

4-(3′,5′-dimethylphenyl)-2-methylindene (5.6 g, 24 mmol) was dissolvedin 80 mL of pentane. To this solution was added 9.6 mL of n-BuLi (2.5Min hexane) and the reaction was allowed to stir 4 hours at roomtemperature. A white solid precipitated from solution and was collectedby frit filtration and washed with additional pentane. Yield was 4.5 g(80%).

9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-isopropylindene

9,9-dichloro-9-silafluorene (1.4 g, 11 mmol) was dissolved in 80 mL ofTHF. To this solution was slowly added lithium4-(3′,5′-dimethylphenyl)-2-methylindene (3.0 g, 11 mmol) as a dry powderand the solution was stirred overnight. After this time, the solvent wasremoved in vacuo and the residue was taken up in diethyl ether. Thesolution was filtered through frit to remove LiCl and the solvent wasremoved in vacuo and used as a crude product (2.1 g) for the next step.

[9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-isopropylindene]ZrCl₂

The crude solid from the previous step (2.1 g, 3.2 mmol) was taken up in50 mL of diethyl ether. To this solution was slowly added n-BuLi (2.56mL, 2.5 M in hexane) and then stirred for 3 hours at room temperature.The solution was cooled to −30° C. and ZrCl₄ (0.74 g, 3.2 mmol) wasadded as a dry powder and stirred at room temperature for ₂ hours. Thesolvent was removed in vacuo and toluene was added to the crude residue.The solution was filtered to remove LiCl. The filtrate was concentratedand pentane was added under heating. The solution was cooled to inducecrystallization. Yield of pure rac/meso metallocene was 120 mg (3.8%).

Supported Metallocene Catalyst System 5 Rac/meso[9-silafluorenebis(4-(3′,5′-dimethylphenyl)2-isopropylindene]zirconiumdichloride/MAO

In a 100 mL round bottom flask rac/meso[9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-isopropylindene]zirconiumdichloride (0.076 g) was added to the MAO solution (6.74 g, 7.2 mL) andstirred twenty minutes. This was filtered through a medium glass fritfunnel and washed with toluene (14 mL). To the combined filtrates wasadded dehydrated silica (4.0 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for twenty minutes, then dried at40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was further dried a total of about₂hours and thirty minutes. The supported catalyst was recovered as adull purple, free flowing solid (5.06 g).

Example 6 rac-9-silafluorenebis(2-methylindenyl)zirconium dimethyl9-Silafluorene, 9,9-bis-2-Methylindene

Solid 2-Methylindenyl lithium (3.34 g, 24.52 mmol) was added to astirred solution of 9,9-Dichloro,9-silafluorene (3.08 g, 12.26 mmol) inEt₂O (ca. 25 mL) and the resultant mixture was stirred at roomtemperature for 2hours. The solvent was removed and the residue wasextracted into CH₂Cl₂ (ca. 75 mL), filtered and the solvent removedgiving a white powder which was washed with pentane (ca 50 mL) and driedunder vacuum leaving 9-Silafluorene, 9,9-bis-2-Methylindene as a whitepowder (3.80 g, 71%).

Preparation of 9-Silafluorene, 9,9-bis-2-Methylindenyl dilithium

A slurry of 9-Silafluorene, 9,9-bis-2-Methylindene (3.80 g, 8.66 mmol)in Et₂O (ca. 25 mL) was treated with n-butyllithium (12 mL of a 1.6 Msolution in hexanes) and the resultant mixture stirred for 1 hour atroom temperature producing a pale yellow precipitate. The mixture wasfiltered to isolate the pale yellow solid which was dried under vacuumgiving 9-Silafluorene, 9,9-bis-2-Methylindenyl dilithium.(Et₂O)_(0.5)(3.80 g, 88%).

Preparation of 9-Silafluorene,9,9-bis-2-Methylindenyl Zirconium Dimethyl

A mixture of 9-Silafluorene, 9,9-bis-2-Methylindenyldilithium.(Et₂)_(0.5) (1.83 g, 3.69 mmol) and ZrCl₄ (0.95 g, 4.08 mmol)in benzene (ca. 25 mL) was stirred for 80 minutes at room temperatureproducing an orange solid. The mixture was filtered and the orange solidwas washed with hexane. Upon mixing with the benzene filtrate, thehexane wash produced a yellow solid and this mixture was filtered toremove the yellow solid. The solvents were removed from the resultingbenzene-hexane filtrate producing an orange solid. The second orangesolid was washed once with benzene and twice with pentane and driedunder vacuum. A slurry of this orange solid in benzene (ca. 10 mL) wastreated with CH₃MgBr (0.8 mL of a 3.0 M solution in Et₂O) and themixture was stirred for 15 minutes at room temperature. Dioxane (ca. 2-3mL) was added to the mixture which was filtered to produce a clearyellow filtrate. The solvents were removed from the filtrate undervacuum giving pure rac-9-Silafluorene,9,9-bis-2-Methylindenyl ZirconiumDimethyl (0.035 g, 1.7%).

Polymerizations Isotactic Polypropylene Homopolymer

The polymerization procedure for producing homopolymers with thesupported catalyst systems prepared as described above (except forExample 6 which is described below) was as follows. In a clean, dry twoliter autoclave which had been flushed with propylene vapor, TEALscavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at this pointif indicated. The quantity of hydrogen is 1.55 millimoles for each psiadded as shown in the Tables. The reactor was closed and filled with 800mL liquid propylene. After heating the reactor to the indicatedpolymerization temperature, the catalyst was added by washing in withpropylene (200 mL). After the indicated time, typically one hour, thereactor was cooled, and the excess propylene vented. The polymer wasremoved and dried.

Polymerization Using rac-9-silafluorenebis(2-methylindenyl)zirconiumdimethyl as Catalyst Precursor—Isotactic Polypropylene HomopolymerProcedure

A solution of triisobutylaluminum (TIBAL) scavenger (0.3 mL of a 10% byvolume solution in toluene) in toluene ( 0.7 mL) was added to a dryclean two liter autoclave under a nitrogen purge. The autoclave wasfilled with 300 mL of liquid propylene and heated to 60° C. Thecatalyst, formed by reacting the catalyst precursor and thetrityltetrakisperfluorophenylborate activator in equimolar amounts intoluene (ca. 1-1.5 mL) for a period of five minutes, was flushed intothe autoclave with 100 mL of propylene. The polymerizations were carriedout for fifteen minutes after which the reactor was cooled and theexcess propylene was vented. The polymer was removed and dried.

Random copolymer (RCP)

The polymerization procedure for producing random copolymers with thesupported catalyst systems prepared as described above was as follows.In a clean, dry two liter autoclave which had been flushed withpropylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gaswas added at this point if indicated. The quantity of hydrogen is 1.55millimoles for each psi added as shown in the Tables. The reactor wasclosed and filled with 800 mL liquid propylene. After heating thereactor to 60° C., a partial pressure of ethylene was added as indicatedand then the catalyst was added by washing in with propylene (200 mL).Ethylene gas was fed to maintain a constant pressure. After theindicated time, typically one hour, the reactor was cooled, and theexcess propylene and ethylene vented. The polymer was removed and dried.

Impact Copolymers (ICP)

The polymerization procedure for producing ICP with the supportedcatalyst systems prepared as described above was as follows. In a clean,dry two liter autoclave which had been flushed with propylene vapor,TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at thispoint. The quantity of hydrogen is 1.55 millimoles for each psi added asshown in the Tables. The reactor was closed and filled with 800 mLliquid propylene. After heating the reactor to 70° C., the catalyst wasadded by washing in with propylene (200 mL). After the indicated time,typically one hour, the reactor was vented to about 170 psig pressureand then an ethylene/propylene gas mixture was passed through thereactor at the rates indicated while maintaining 200 psig. At the end ofthe gas phase stage, typically 90 to 150 minutes, the reactor was ventedand cooled under N₂. The granular ICP polymer was removed and dried.

Polymerization run numbers 1-14 were made using Supported ComparisonMetallocene Catalyst System 1. Results are reported in Tables 1 and 2.

Polymerization run numbers 15-25 made using Supported ComparisonMetallocene Catalyst System 2 Results are reported in Tables 3 and 4.

Polymerization run numbers 65-71 were made using Supported MetalloceneCatalyst System 3. Results are reported in Tables 5 and 6.

Polymerization run numbers 72-88 were made using Supported MetalloceneCatalyst System 4. Results are reported in Tables 7 and 8.

Polymerization run numbers 133 and 134 were made using SupportedMetallocene Catalyst System 5. Results are reported in Tables 9 and 10.

Polymerization run numbers 135 and 136 were made using MetalloceneCatalyst System 6. Results are reported in Table 11.

Polymer Analysis

Molecular weight determinations were made by gel permeationchromatography (GPC) according to the following technique. Molecularweights and molecular weight distributions were measured using a Waters150C gel permeation chromatography equipped with Shodex (Showa Denko)AT-806MS columns and a differential refractive index (DRI) detectoroperating at 145° C. with 1,2,4-trichlorobenzene as the mobile phase ata 1.0 mL/min. flow rate. The sample injection volume was 300microliters. The columns were calibrated using narrow polystyrenestandards to generate a universal calibration curve. The polypropylenecalibration curve was established using k=8.33×10⁻⁵ and a=0.800 as theMark-Houwink coefficients. The numerical analyses were performed usingWaters “Expert-Ease” software running on a VAX 6410 computer.

Ethylene amounts in the random copolymers were determined by FT-IR usinga calibration obtained from samples whose composition was determined byNMR.

DSC melting points were determined on commercial DSC instruments and arereported as the second melting point. The polymer granules weighing lessthan 10 milligrams were heated to 230.0° C. for ten minutes and thencooled from 230° C. to 50° C. at 10° C./minute. The sample is held at50° C. for five minutes. The second melt is then recorded as the sampleis heated from 50° C. to 200° C. at a rate of 10° C./minute. The peaktemperature is recorded as the second melting point.

ICP Polymer Extraction Method

The ICP polymer was dissolved in hot xylene and then allowed to coolovernight. After filtration the insolubes are dried. The xylene solubleportion was evaporated and the soluble material recovered. The IV of therecovered soluble material was measured in decalin at 135° C. by usingknow methods and instruments such as a Schott A VSPro ViscosityAutomatic Sampler.

At very high ICP MFR this method can extract some low molecular weightisotactic PP and thus lower the observed IV.

ICP Polymer Fractionation Method

The ICP samples were sent to Polyhedron Laboratories, Inc. to befractionated and analyzed by GPC. A generally described of the procedureis found in the reference J. C. Randall, J. Poly. Sci.: Part A PolymerChemistry, Vol. 36, 1527-1542 (1998).

TABLE 1 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)₂ zirconiumdichloride/MAO - comparison Metallocene Catalyst Cat Time C₂ ⁼/C₃ ⁼System TEMP. Amount Yield Efficiency C2 = H2 split flow rates RUN #(Comparison) (° C.) (mg) (g) (Kg/g cat) (delta psi) (delta psi) (min.)(l/min.) 1 1 60 67 274.7 4.10  0  0 60 — 2 1 60 45 71.7 1.59  0  0 60 —3 1 60 40 134.1 3.35 10  0 60 — 4 1 60 42 221.5 5.27 20  0 60 — 5 1 6030 121.3 4.04 55  0 60 — 6 1 60 30 130.2 4.34 70  0 60 — 7 1 60 30 101.83.39 20  0 60 — 8 1 70 45 293.5 6.52 — 50 60 — 9 1 70 31 198.9 6.42 — 5060 — 10  1 70 30 291.9 9.73 — 50  60/150 4.0/1.0 11  1 70 30 231.3 7.71— 50 60/90 4.0/1.0 12  1 70 30 224.8 7.49 — 50 60/90 4.1/0.9 13  1 70 30209.9 7.00 — 50 60/90 3.6/1.4 14  1 70 30 208.2 6.94 — 50 60/90 4.0/1.0

TABLE 2 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)₂ zirconiumdichloride/MAO - comparison Metallocene Catalyst Total Ethylene TotalMelting System Ethylene in Rubber Rubber Final MFR Point IV Of RUN #(Comparison) (wt %) (wt %) (wt %) (g/10 min.) (° C.) MW MWD Copolymer 11 — — — 0.16 149.2 600.0 2.00 — 2 1 — — — 0.54 148.2 664.9 1.92 — 3 10.67 — — 0.84 142.0 349.0 2.09 — 4 1 1.28 — — 2.57 138.4 280.0 1.95 — 51 3.77 — — 6.48 121.4 255.0 2.04 — 6 1 4.43 — — 5.95 116.0 301.0 2.30 —7 1 1.44 — — 2.05 137.5 330.4 2.23 — 8 1 — — — 99.6 150.3 120.6 3.01 — 91 — — — 58.95 150.9 135.7 3.15 — 10  1 13.23 49.20 26.89 178.5 151.281.2 3.37 0.7520 11  1 7.58 47.37 16.00 134.05 150.6 98.4 3.25 0.687 12 1 7.82 50.04 15.63 127.16 150.0 100.4 3.11 0.708 13  1 5.3 38.96 13.60201.9 150.43 91.2 3.28 0.779 14  1 0.47 64.32 0.73 97.1 150.8 116.8 3.42not submit.

TABLE 3 racemicdimethylsiladiyl(2-methyl-4-[1-naphthy]indenyl)₂zirconiumdichloride/MAO - comparison Metallocene Catalyst Cat Time C₂ ⁼/C₃ ⁼System Amount Yield Efficiency C2 = H2 split flow rates RUN #(comparison) (mg) (g) (Kg/g cat) (delta psi) (delta psi) (min.) (l/min.)15 2 76 332.0 4.37 — 40 60 — 16 2 61 260.8 4.28 — 35 60/120 4.0/1.0 17 260 266.2 4.44 — 35 60/120 4.4/0.6 18 2 60 272.6 4.54 — 35 60/120 4.2/0.819 2 61 196.9 3.23 — 35 60 — 20 2 61 121.2 1.99 20  5 60 — 21 2 61 118.11.94 30  5 60 — 22 2 61 137.7 2.26 40  5 60 — 23 2 62 141.9 2.29 50  560 — 24 2 60 138.6 2.31 40 10 60 — 25 2 62 234.8 3.79 — 50 60/90 4.0/1.0

TABLE 4 racemicdimethylsiladiyl(2-methyl-4-[1-naphthy]indenyl)₂zirconiumdichloride/MAO - comparison Metallocene Catalyst Total Ethylene TotalMelting System Ethylene in Rubber Rubber Final MFR Point IV of RUN #(comparison) (wt %) (wt %) (wt %) (g/10 min.) (° C.) MW MWD Copolymer 152 — — — 4.08 150.5 299.1 2.78 — 16 2 7.76 47.27 16.42 4.76 151.7 212.12.68 1.6567 17 2 16.39 61.45 26.67 1.3 150.8 230.9 3.33 1.7048 18 2 9.7451.52 18.91 4.98 151.0 210.4 2.96 1.7127 19 2 — — — 3.12 151.0 278.02.49 — 20 2 1.27 — — 0.19 138.43 603.0 2.59 — 21 2 1.75 — — 0.15 136.10614.8 2.59 — 22 2 2.25 — — 0.196 131.90 604.5 2.31 — 23 2 2.82 — — 0.213127.83 579.0 2.36 — 24 2 2.39 — — 0.225 131.63 542.8 2.41 — 25 2 3.80348.39  7.86 4.95 151.43 176.8 2.94 1.425 

TABLE 5racemic[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-methylindenYL]zirconiumdichloride/MAO Metallocene Cat Time C₂ ⁼/C₃ ⁼ Catalyst Amount TEMP.Yield Efficiency H2 split flow rates RUN # System (mg) (° C.) (g) (Kg/gcat) (delta psi) (min.) (l/min.) 65 3 299  60 13.2 0.04  0  6 — 66 3 6160 35.0 0.57  0 60 — 67 3 60 60 81.3 1.4 35 60 — 68 3 32 70 96.2 3.0 3560/90  4.0/1.0 69 3 30 70 93.3 3.1 35 60/120 4.0/1.0 70 3 31 70 83.9 2.735 60/90  3.6/1.4 71 3 30 70 77.8 2.6 35 60/120 4.2/0.8

TABLE 6racemic[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-methylindenyl]zirconiumdichloride/MAO Metallocene Total Ethylene Total Melting CatalystEthylene in Rubber rubber Final MFR Point IV of RUN # System (wt %) (wt%) (wt %) (g/10 min.) (° C.) MW MWD Copolymer 65 3 — — — 0.65 156.17 412149.3 — 66 3 — — — 0.075 156.23 710.8 2.71 — 67 3 — — — 3.59 156.5 270.72.82 — 68 3 4.814 54.74 8.8 69.59 155.43 119.4 3.22 69 3 6.624 49.5513.4 9.84 156.5 200.0 3.56 70 3 3.095 42.72 7.2 14.54 155.97 194.5 3.5271 3 7.691 54.36 14.1 10.61 157.17 207.1 3.50

TABLE 7racemic[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindenyl]zirconiumdichloride/MAO Metallocene Cat Time C₂ ⁼/C₃ ⁼ Catalyst Amount TEMP.Yield Efficiency C2 = H2 split flow rates RUN # System (mg) (° C.) (g)(Kg/g cat) (delta psi) (delta psi) (min.) (l/min.) 72 4 300  60 11.80.04 —  0 10 — 73 4 120  70 116.8 0.97 — 10 60 — 74 4 121  70 127.6 1.1— 10 60/90  4.0/1.0 75 4 62 70 126.4 2.0 — 20 60 — 76 4 63 70 139.5 2.2— 35 60 — 77 4 60 70 151.4 0.40 — 20 60/90  4.2/0.8 78 4 62 70 246.2 4.0— 35 60/90  4.2/0.8 79 4 60 70 218.9 3.6 — 35 60/120 4.2/0.8 80 4 62 70249.8 4.0 — 50 60 — 81 4 61 70 233.1 3.8 — 35 60/120 4.4/0.6 82 4 61 60184.2 3.0 10 20 60 — 83 4 60 60 202.6 3.4 20 20 60 — 84 4 60 60 209.63.5 30 20 60 — 85 4 60 70 157.9 2.6 — 35 30/120 4.4/0.6 86 4 63 70 200.53.2 — 35 60 — 87 4 60 70 223.9 3.7 — 35 60/120 4.2/0.8 88 4 60 70 196.13.3 — 35 60/180 4.2/0.8

TABLE 8racemic[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindenyl]zirconiumdichloride/MAO Metallocene Total Ethylene Total Melting CatalystEthylene in Rubber rubber Final MFR Point IV of RUN # System (wt %) (wt%) (wt %) (g/10 min.) (° C.) MW MWD Copolymer 72 4 — — — 0.82 160.78381.6 2.01 — 73 4 — — — 2.85 159.17 267.3 1.80 — 74 4 4.297 32.93 13.0 3.56 161.1 255.7 2.03 2.92 75 4 — — — 11.53 158.83 191.5 2.25 — 76 4 — —— 24.03 159.43 166.6 1.98 — 77 4 2.449 32.63 7.5 12.0 159.7 194.7 2.112.06 78 4 2.012 42.53 4.7 110.44 159.1 116.8 2.48 2.21 79 4 3.389 40.388.4 32.37 158.5 173.2 2.71 2.55 80 4 — — — 499.99 157.9 85.7 2.25 — 81 44.093 47.35 8.6 41.24 158.57 147.0 2.32 2.87 82 4 0.87  — — 9.54 151.17204.2 2.39 — 83 4 1.4  — — 18.53 146.17 182.3 2.14 — 84 4 2.4  — — 24.5138.5 172.2 1.93 — 85 4 4.732 46.4  10.2  118.7 158.23 119.7 2.39 86 4 —— — 28.17 158.37 — 87 4 3.081 44.21 7.0 61.24 158.83 88 4 — — — 15.7158.77 —

TABLE 9 [9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-isopropylindene]zirconium dichloride/MAO Metal- locene Cat H2 RUN Catalyst TEMP. AmountYield Efficiency (delta Time # System (° C.) (mg) (g) (Kg/g cat) psi)(min.) 133 5 60 302 6.0 0.02  0 60 134 5 70 121 18.4 0.15 10 60

TABLE 10 [9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-isopropylindene]zirconium dichloride/MAO Metallocene Catalyst Final MFR Melting PointRUN # System (g/10 min.) (° C.) MW MWD 133 5 — 150.9, 467.6 4.98 minor156.52 134 5 32.07 156.5 104.8 2.71

TABLE 11 Polymerization using rac-9-silafluorenebis(2-methylindenyl)zirconium dimethyl Catalyst Melting Run T Precursor Activator YieldPoint # (° C.) (mg) (mg) (g) (° C.) MW MWD 135 60 1.20 1.98 49.3 148.772610 1.93 136 60 0.90 1.50 50.4 149.8 72215 1.97

While the present invention has been described and illustrated byreference to particular embodiments, it will be appreciated by those ofordinary skill in the art, that the invention lends itself to manydifferent variations not illustrated herein. For these reasons, then,reference should be made solely to the appended claims for purposes ofdetermining the true scope of the present invention.

We claim:
 1. A supported catalyst system comprising the product of oneor more support materials, one or more activators and one or morecompounds represented by the formula:

wherein: M¹ is selected from the group consisting of titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenumand tungsten; R¹ and R² are identical or different, and are one of ahydrogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀aryl group, a C₆-C₁₀ aryloxy group, a C₂-C₄₀ alkenyl group, a C₇-C₄₀arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group,an OH group or a halogen atom, or are a conjugated diene which isoptionally substituted with one or more hydrocarbyl,tri(hydrocarbyl)silyl groups or tri(hydrocarbyl)silylhydrocarbyl groups,said diene having up to 30 atoms not counting hydrogen; R³ are identicalor different and are each a halogen atom, a C₁-C₁₀ alkyl group which maybe halogenated, a C₆-C₁₀ aryl group which may be halogenated, a C₂-C₁₀alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀ alkylaryl group, aC₈-C₄₀ arylalkenyl group, a —NR′₂, —SR′, —OR′, —OSiR′₃ or —PR′₂ radical,wherein: R′ is one of a halogen atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀aryl group; R⁴ to R⁷ are identical or different and are hydrogen, or asdefined for R³ or two or more adjacent radicals R⁵ to R⁷ together withthe atoms connecting them form one or more rings; R¹³ is represented bythe formula:

wherein R¹⁷ to R²⁴ are as defined for R¹ and R², or two or more adjacentradicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with the atomsconnecting them form one or more rings; M² is carbon, silicon, germaniumor tin; and R⁸, R⁹, R¹⁰, R¹¹ and R¹² are identical or different and havethe meanings stated for R⁴ to R⁷.
 2. The supported catalyst system ofclaim 1 wherein R³ are identical C₁-C₄ alkyl groups.
 3. The supportedcatalyst system of claim 1 wherein R⁴ to R⁷ and R¹⁴ to R¹⁶ are hydrogenatoms.
 4. The supported catalyst system of claim 1 wherein R³ are bothC₃ alkyl groups.
 5. The supported catalyst system of claim 1 wherein M²is silicon.
 6. The supported catalyst system of claim 1 wherein R¹²-R²⁴are hydrogen.
 7. The supported catalyst system of claim 1 wherein theactivator comprises one or more non-coordinating anion activators. 8.The supported catalyst system of claim 1 wherein the activator comprisesone or more alkylalumoxane activators.
 9. The supported catalyst systemof claim 1 wherein the activator comprises a non-coordinating anionactivator and an alkylalumoxane activator.
 10. The supported catalystsystem of claim 1 wherein the support material comprises magnesiumchloride, silica or a combination thereof.